Dye mixtures of fiber reactive azo dyes, production and use

ABSTRACT

The invention relates to reactive dye mixtures containing one or several dyes of general formula (I), one or several dyes of general formula (II) and, optionally, one or several dyes or general formula (IIIa)-(IIIf), wherein D 1 -D 8 , R, R 1 —R 39 , Z, Z 1 -Z 3  and M have the meaning as cited in claim 1. The invention also relates to the production and the use thereof in order to dye and print fibrous material containing hydroxy and/or carbonamide groups.

This invention relates to the technical field of fiber-reactive azo dyes.

Mixed fiber-reactive azo dyes and their use for dyeing hydroxyl- and carboxamido-containing material in black shades are known for example from the documents U.S. Pat. No. 5,445,654, U.S. Pat. No. 5,611,821, KR 94-2560, Sho 58-160362 and EP-A-0 870 807. However, they have certain application defects, such as for example an overly large dependence of the color yield on varying dyeing parameters in the dyeing process or an insufficient or unlevel color build-up on cotton (good color build-up results from the ability of a dye to provide a proportionally stronger dyeing when used in higher concentrations in the dyebath), or an excessive salt dependence of the dyeings. Consequences of these defects can be poor reproducibilities for the dyeings that are obtainable. The documents WO 98/42784, WO 98/42785, WO 93/18224 and U.S. Pat. No. 5,330,539 disclose dyes and dye mixtures which can be dyed in the presence of small amounts of salt, but which provide only very weak dyeings in the absence of salt.

Since it is commercially as well as environmentally necessary to reduce the salt content of dyeing effluent, there is a need for reactive dyes which provide dyeings of high color strength in the presence of small amounts of salt or even in the absence of electrolyte salts.

The present invention, then, provides dye mixtures which provide dyeings of high color strength in the presence of only very low levels or even in the absence of electrolyte salts.

The invention accordingly provides dye mixtures comprising one or more, such as two or three, preferably 1 or 2, dyes of the hereinbelow indicated and defined general formula (I)

one or more, such as two or three, preferably 1 or 2, dyes of the hereinbelow indicated and defined general formula (II)

and, optionally, as further components for blending or shading, one or more, such as two or three, preferably 1 or 2, dyes having, for example, the hereinbelow indicated and defined general formulae (IIIa)-(IIIf)

where:

-   -   D¹ and D² are each a group of the general formula (1)         where         -   R¹ is hydrogen, (C₁-C₄)-alkyl, aryl or a substituted aryl             radical;         -   R² and R³ are independently hydrogen, (C₁-C₄)-alkyl,             (C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen;             and         -   A is a phenylene group of the general formula (2)             -   where             -   R⁴ and R⁵ are independently hydrogen, (C₁-C₄)-alkyl,                 (C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido or                 halogen; or         -   a naphthylene group of the general formula (3)             -   where             -   R⁶ and R⁷ are independently hydrogen, (C₁-C₄)-alkyl,                 (C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido or                 halogen; or         -   a polymethylene group of the general formula (4)             —(CR⁸R⁹)_(k)—  (4)             -   where             -   k is an integer greater than 1 and             -   R⁸ and R⁹ are independently hydrogen, (C₁-C₄)-alkyl,                 (C₁-C₄)-alkoxy, hydroxyl, cyano, amido, halogen or aryl;                 and         -   X¹ is hydrogen or a group of the formula —SO₂-Z; or     -   are each a phenyl group of the general formula (5)         -   where         -   R¹⁰ and R¹¹ are independently hydrogen, (C₁-C₄)-alkyl,             (C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen;             and         -   X² has one of the meanings of X¹;     -   or are each a naphthyl group of the general formula (6)         -   where         -   R¹² and R¹³ are independently hydrogen, (C₁-C₄)-alkyl,             (C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen;             and         -   X³ has one of the meanings of X¹;     -   Z is —CH═CH₂, —CH₂CH₂Z¹ or hydroxyl,         -   where         -   Z¹ is hydroxyl or an alkali-eliminable group; and     -   M is hydrogen, an alkali metal or one equivalent of an alkaline         earth metal;     -   D³ has one of the meanings of D¹ or D² or is a group of the         general formula (7)         -   where         -   R²¹ and R²² independently have one of the meanings of R² and             R³;         -   R²³ is hydrogen, (C₁-C₄)-alkyl, unsubstituted or             (C₁-C₄)-alkyl-, (C₁-C₄)-alkoxy-, sulfo-, halogen- or             carboxyl-substituted phenyl; and         -   Z²¹ is a fiber-reactive group of the general formula (8)             or (9) or (10)             -   where             -   V is fluorine or chlorine;             -   U¹ and U² are independently fluorine, chlorine or                 hydrogen; and             -   Q¹ and Q² are independently chlorine, fluorine,                 cyanamido, hydroxyl, (C₁-C₆)-alkoxy, phenoxy,                 sulfophenoxy, mercapto, (C₁-C₆)-alkyl mercapto,                 pyridino, carboxypyridino, carbamoylpyridino or a group                 of the general formula (11) or (12)                 -   where                 -   R^(2′) is hydrogen or (C₁-C₆)-alkyl,                     sulfo-(C₁-C₆)-alkyl, or phenyl which is                     unsubstituted or substituted by (C₁-C₄)-alkyl,                     (C₁-C₄)-alkoxy, sulfo, halogen, carboxyl, acetamido                     or ureido;             -   R^(3′) and R^(4′) independently have one of the meanings                 of R^(2′), or combine to form a cyclic ring system of                 the formula —(CH₂)_(j)—, where j is 4 or 5, or                 alternatively —(CH₂)₂-E-(CH₂)₂—, where E is oxygen,                 sulfur, sulfo, —NR^(5′)—, where R^(5′) is equal to                 (C₁-C₆)-alkyl, or they are a group of the general                 formula (13)                 -   where                 -   R²⁴, R²⁵ and R²⁶ are each (C₁-C₄)-alkyl or                     (C₁-C₄)-hydroxyalkyl; and                 -   B⁻ is the equivalent of an anion, such as                     hydrogensulfate, sulfate, fluoride, chloride,                     bromide, dihydrogenphosphate, hydrogenphosphate,                     phosphate, hydroxide or acetate;             -   W is phenylene which is unsubstituted or substituted by                 1 or 2 substituents, such as (C₁-C₄)-alkyl,                 (C₁-C₄)-alkoxy, carboxyl, sulfo, chlorine, bromine, or                 is (C₁-C₄)-alkylene-arylene or (C₂-C₆)-alkylene, which                 can be interrupted by oxygen, sulfur, sulfo, amino,                 carbonyl, carboxamido, or is phenylene-CONH-phenylene,                 which is unsubstituted or substituted by (C₁-C₄)-alkyl,                 (C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido, ureido                 or halogen, or is naphthylene, which is unsubstituted or                 substituted by one or two sulfo groups; and             -   Z is as defined above;     -   R is hydrogen, (C₁-C₄)-alkyl or phenyl which is unsubstituted or         substituted by (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, sulfo, halogen,         carboxyl, acetamido or ureido;         -   or         -   is a group of the formula (14)             CH₂—SO₃M   (14),             -   where M is as defined above; and     -   n is 1 or 2,     -   D⁴, D⁵, D⁶, D⁷ and D⁸ have one of the meanings of D¹, D² or D³,         and, if R³¹ is not a group of the general formula (8) or (9),         D⁴, and also D⁵ or D5 and D⁸, contain at least one         fiber-reactive group of the formula —SO₂Z or Z²¹;     -   R³¹ is hydrogen, acetyl, carbamoyl, sulfomethyl or a group of         the general formula (8) or (9),     -   R³² is hydrogen or sulfomethyl,     -   R³³ is methyl, carboxyl or carboxyalkyl, with C₁-C₄-alkyl,     -   R³⁴ is hydrogen or methyl,     -   R³⁵ is hydrogen, cyano, carbamoyl, carboxyl or sulfomethyl,     -   R³⁶ is methyl, ethyl or β-sulfoethyl,     -   R³⁷ is methyl, carboxyl or carboxyalkyl, with C₁-C₄-alkyl,     -   R³⁸ is acetamido, ureido or methyl,     -   R³⁹ is hydrogen, methyl or methoxy,     -   m is 0 or 1,     -   p is 1, 2 or3, and     -   Z³ has one of the meanings of Z²¹.

In the general formula (I) at least one of D¹ and D² is a group of the general formula (1);

-   -   when A is a group of the general formula (4), R¹ is aryl or         substituted aryl; and the reactive dye of the general         formula (I) contains at least one —SO₂-Z group.

The dyes of the general formula (II) contain independently of one another at least one fiber-reactive group of the formula —SO₂-Z or Z²¹.

The individual symbols in the general formulae above and below can have identical or different meanings under their definition, irrespective of whether the symbols bear the same or a different designation.

(C₁-C₄)-Alkyl R may be straight-chain or branched and is in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl. Methyl and ethyl are preferred. The same logic applies to (C₁-C₄)-alkoxy groups.

Aryl R is in particular phenyl. Substituted aryl R¹ is in particular phenyl substituted by one, two or three independent groups selected from the group consisting of (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido and halogen.

Halogen R is in particular fluorine, chlorine or bromine, and fluorine and chlorine are preferred.

Alkali-eliminable Z¹ in the β-position of the ethyl group of Z includes for example halogen atoms, such as chlorine and bromine, ester groups of organic carboxylic and sulfonic acids, as of alkylcarboxylic acids, substituted or unsubstituted benzenecarboxylic acids and substituted or unsubstituted benzenesulfonic acids, such as alkanoyloxy of 2 to 5 carbon atoms, especially acetyloxy, benzoyloxy, sulfobenzoyloxy, phenylsulfonyloxy and toluylsulfonyloxy, also acidic ester groups of inorganic acids, as of phosphoric acid, sulfuric acid and thiosulfuric acid (phosphato, sulfato and thiosulfato groups), similarly dialkylamino groups having alkyl groups of 1 to 4 carbon atoms in each case, such as dimethylamino and diethylamino.

Z is preferably vinyl, β-chloroethyl and particularly preferably β-sulfatoethyl.

The groups “sulfo”, “carboxyl”, “thiosulfato”, “phosphate” and “sulfato” include not only their acid form but also their salt form. Accordingly, sulfo groups are groups conforming to the general formula —SO₃M, thiosulfato groups are groups conforming to the general formula —S—SO₃M, carboxyl groups are groups conforming to the general formula —COOM, phosphate groups are groups conforming to the general formula —OPO₃M₂ and sulfato groups are groups conforming to the general formula —OSO₃M, in each of which M is as defined above.

The dyes of the general formula (I) to (III) may possess different fiber-reactive groups —SO₂Z within the meaning of Z. More particularly, the fiber-reactive groups —SO₂Z may be on the one hand vinylsulfonyl groups and on the other —CH₂CH₂Z¹ groups, preferably β-sulfatoethylsulfonyl groups. If the dyes of the general formula (I) to (III) contain vinylsulfonyl groups in some instances, then the fraction of the respective dye with the vinylsulfonyl group is up to about 30 mol %, based on the respective amount of total dye.

Alkali M is in particular lithium, sodium or potassium. M is preferably hydrogen or sodium.

R¹ to R¹³ are each preferably hydrogen and R⁶, R⁷, R¹² and R¹³ are each preferably sulfo as well.

When A is phenylene and X¹ is —SO₂Z, the SO₂Z group is preferably disposed meta or para relative to the nitrogen atom. In the group of the general formula (1), the carboxamide group is preferably disposed para or meta relative to the diazo group. When A is naphthylene, the bond leading to the nitrogen atom is preferably attached to the naphthalene nucleus in the β-position. When D¹ or D² is a group of the general formula (6), then the bond which leads to the diazo group is preferably attached to the naphthalene nucleus in the β-position.

When D¹ or D2 is a group of the general formula (5) and X² is —SO₂Z, then the SO₂Z group is preferably disposed meta or para relative to the diazo group.

Examples of substituents A are in particular 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2-chloro-1,4-phenylene, 2-chloro-1,5-phenylene, 2-bromo-1,4-phenylene, 2-sulfo-1,4-phenylene, 2-sulfo-1,5-phenylene, 2-methoxy-1,5-phenylene, 2-ethoxy-1,5-phenylene, 2,5-dimethoxy-1,4-phenylene, 2-methoxy-5-methyl-1,4-phenylene, 2-methyl-1,4-phenylene, 2,6-naphthylene, 2,8-naphthylene, 1-sulfo-2,6-naphthylene, 6-sulfo-2,8-naphthylene or 1,2-ethylene and 1,3-propylene.

A is particularly preferably 1,3-phenylene, 1,4-phenylene, 2-sulfo-1,4-phenylene, 2-methoxy-1,5-phenylene, 2,5-dimethoxy-1,4-phenylene, 2-methoxy-5-methyl-1,4-phenylene or 1,2-ethylene and 1,3-propylene, and in the case of the two last-mentioned alkylene groups R¹ is preferably phenyl or 2-sulfophenyl.

k is preferably 2 or 3.

Examples of groups D¹ to D⁸ of the general formulae (5) and (6) are 2-(β-sulfato-ethylsulfonyl)phenyl, 3-(β-sulfatoethylsulfonyl)phenyl, 4-(β-sulfatoethylsulfonyl)-phenyl, 2-carboxy-5-(β-sulfatoethylsulfonyl)phenyl, 2-chloro-4-(β-sulfatoethyl-sulfonyl)phenyl, 2-chloro-5-(β-sulfatoethylsulfonyl)phenyl, 2-bromo-4-(β-sulfato-ethylsulfonyl)phenyl, 2-sulfo-4-(β-sulfatoethylsulfonyl)phenyl, 2-sulfo-5-(β-sulfato-ethylsulfonyl)phenyl, 2-methoxy-5-(β-sulfatoethylsulfonyl)phenyl, 2-ethoxy-5-(β-sulfatoethylsulfonyl)phenyl, 2,5-dimethoxy-4-(β-sulfatoethylsulfonyl)phenyl, 2-methoxy-5-methyl-4-(β-sulfatoethylsulfonyl)phenyl, 2-methyl-4-(β-sulfatoethyl-sulfonyl)phenyl, 2- or 3- or 4-(β-thiosulfatoethylsulfonyl)phenyl, 2-methoxy-5-(β-thiosulfatoethylsulfonyl)phenyl, 2-sulfo-4-(β-phosphatoethylsulfonyl)phenyl, 2- or 3- or 4-vinylsulfonylphenyl, 2-sulfo-4-vinylsulfonylphenyl, 2-chloro-4-(β-chloro-ethylsulfonyl)phenyl, 2-chloro-5-(β-chloroethylsulfonyl)phenyl, 3- or 4-(β-acetoxyethylsulfonyl)phenyl, 6- or 8-(β-sulfatoethylsulfonyl)naphth-2-yl, 6-(β-sulfatoethylsulfonyl)-1-sulfonaphth-2-yl and 8-(β-sulfatoethylsulfonyl)-6-sulfo-naphth-2-yl, preferably 3-(β-sulfatoethylsulfonyl)phenyl, 4-(β-sulfatoethylsulfonyl)-phenyl, 2-sulfo-4-(β-sulfatoethylsulfonyl)phenyl, 2-methoxy-5-(β-sulfatoethylsulfonyl)-phenyl, 2,5-dimethoxy-4-(β-sulfatoethylsulfonyl)phenyl, 2-methoxy-5-methyl-4-(β-sulfatoethylsulfonyl)phenyl and 3- or 4-vinylsulfonylphenyl.

In the general formula (II), R is preferably hydrogen or a group of the formula (14), M being as defined above.

In the general formula (II), D³ is preferably 2-(β-sulfatoethylsulfonyl)phenyl, 3-(β-sulfatoethylsulfonyl)phenyl, 4-(β-sulfatoethylsulfonyl)phenyl, 2-sulfo-4-(β-sulfatoethylsulfonyl)phenyl, 2-methoxy-5-(β-sulfatoethylsulfonyl)phenyl, 2,5-dimethoxy-4-(β-sulfatoethylsulfonyl)phenyl, 2-methoxy-5-methyl-4-(β-sulfatoethylsulfonyl)phenyl, 6-(β-sulfatoethylsulfonyl)-1-sulfonaphth-2-yl, 2-,3- or 4-vinylsulfonylphenyl, 1-sulfo-4-(2,4-difluoropyrimidin-6-yl)amino-2-phenyl, 1-sulfo-4-(4,6-difluoropyrimidin-2-yl )amino-2-phenyl, 2-sulfo-4-(2,4-difluoropyrimidin-6-yl)amino-1-phenyl or 2-sulfo-4-(4,6-difluoropyrimidin-2-yl)amino-1-phenyl.

In the general formula (II), where D³ is a group of the general formula (6), the bond leading to the diazo group is preferably attached in β-position to the naphthalene nucleus of (6).

In the general formula (7), R²¹ to R²³ are each preferably hydrogen and R²¹ and R²² are preferably sulfo as well.

In the general formulae (11) and (12), R^(2′) to R^(4′) are each preferably hydrogen or methyl, R^(2′) is preferably phenyl as well and R^(3′) and R^(4′) are each preferably 2-sulfoethyl, 2-, 3- or 4-sulfophenyl, 3- or 4-trimethylammoniophenyl sulfate, 3- or 4-trimethylammoniophenyl chloride, or R^(3′) and R^(4′) combine to form a cyclic ring system which preferably conforms to the formula —(CH₂)₂—O—(CH₂)₂—.

W is preferably 1,3-phenylene, 1,4-phenylene, 2-sulfo-1,4-phenylene, 2-methoxy-1,5-phenylene, 2,5-dimethoxy-1,4-phenylene, 2-methoxy-5-methyl-1,4-phenylene, 1,2-ethylene, 1,3-propylene.

Examples of the groups Q¹ and Q² in the general formula (9) are independently of one another fluorine, chlorine, hydroxyl, methoxy, ethoxy, phenoxy, 3-sulfophenoxy, 4-sulfophenoxy, methylmercapto, cyanamido, amino, methylamino, ethylamino, morpholino, piperidino, phenylamino, methylphenylamino, 2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, 2,4-disulfophenylamino, 2,5-disulfophenylamino, 3-trimethylammoniumphenylamino, 4-trimethylammoniumphenylamino, 2-sulfoethylamino, N-methyl-2-sulfoethylamino, pyridino, 3-carboxypyridino, 4-carboxypyridino, 3-carbamoylpyridino, 4-carbamoylpyridino, 2-(2-sulfatoethylsulfonyl)phenylamino, 3-(2-sulfatoethylsulfonyl)phenylamino, 4-(2-sulfatoethylsulfonyl)phenylamino, N-ethyl-3-(2-sulfatoethylsulfonyl)phenylamino, N-ethyl-4-(2-sulfatoethylsulfonyl)phenylamino, 2-carboxy-5-(2-sulfatoethylsulfonyl)phenylamino), 2-chloro-4-(2-sulfatoethylsulfonyl)phenylamino, 2-chloro-5-(2-sulfatoethylsulfonyl)phenylamino, 2-bromo-4-(2-sulfatoethylsulfonyl)phenylamino, 2-sulfo-4-(2-sulfatoethylsulfonyl)phenylamino, 2-sulfo-5-(2-sulfatoethylsulfonyl)phenylamino, 2-methoxy-5-(2-sulfatoethylsulfonyl)phenylamino, 2,5-dimethoxy-4-(2-sulfatoethylsulfonyl)phenyl-amino, 2-methoxy-5-methyl-4-(2-sulfatoethylsulfonyl)phenylamino, 2-methyl-4-(2-sulfatoethylsulfonyl)phenylamino, 2-(vinylsulfonyl)phenylamino, 3-(vinylsulfonyl)-phenylamino, 4-(vinylsulfonyl)phenylamino, N-ethyl-3-(vinylsulfonyl)phenylamino, N-ethyl-4-(vinylsulfonyl)phenylamino, 6-(2-sulfatoethylsulfonyl)naphth-2-ylamino, 8-(2-sulfatoethylsulfonyl)naphth-2-ylamino, 8-(2-sulfatoethylsulfonyl)-6-sulfonaphth-2-ylamino, 3-(2-(2-sulfatoethylsulfonyl)ethylcarbamoyl)phenylamino, 4-(2-(2-sulfatoethylsulfonyl)ethylcarbamoyl)phenylamino, 3-(2-(vinylsulfonyl)ethyl-carbamoyl)phenylamino, 4-(2-(vinylsulfonyl)ethylcarbamoyl)phenylamino, 4-(N-methyl-2-(2-sulfatoethylsulfonyl)ethylcarbamoyl)phenylamino, 4-(N-phenyl-2-(2-sulfatoethylsulfonyl)ethylcarbamoyl)phenylamino, 4-(3-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)phenylamino, 4-(4-(2-sulfatoethylsulfonyl)phenylcarbamoyl)-phenylamino, 3-(3-(2-sulfatoethylsulfonyl)phenylcarbamoyl)phenylamino, 3-(4-(2-sulfatoethylsulfonyl)phenylcarbamoyl)phenylamino, 3-(2-Sulfatoethylsulfonyl)-propylamino, N-methyl-N-(2-(2-sulfatoethylsulfonyl)ethyl)amino, N-phenyl-N-(2-(2-sulfatoethylsulfonyl)ethyl)amino, N-phenyl-N-(3-(2-sulfatoethylsulfonyl)propyl)-amino.

Preferably the groups Q¹ and Q² in the general formula (9) independently of one another are fluorine, chlorine, cyanamido, morpholino, 2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, 3-trimethylammoniumphenylamino, 4-trimethylammoniumphenylamino, N-methyl-2-sulfoethylamino, 3-carboxypyridino, 4-carboxypyridino, 3-carbamoylpyridino, 4-carbamoylpyridino, 3-(2-sulfatoethylsulfonyl)phenylamino, 4-(2-sulfatoethylsulfonyl)phenylamino, 3-(vinylsulfonyl)phenylamino, 4-(vinylsulfonyl)phenylamino, 4-(3-(2-sulfatoethylsulfonyl)phenylcarbamoyl)phenylamino, 4-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)phenylamino, 3-(3-(2-sulfatoethylsulfonyl)phenylcarbamoyl)-phenylamino, 3-(4-(2-sulfatoethylsulfonyl)phenylcarbamoyl)phenylamino, N-methyl-N-(2-(2-sulfatoethylsulfonyl)ethyl)amino, N-phenyl-N-(2-(2-sulfatoethylsulfonyl)ethyl)amino.

With particular preference the groups Q¹ and Q² in the general formula (9) independently of one another are fluoro, chloro, cyanamido, morpholino, 2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, 3-trimethylammoniumphenylamino, 4-trimethylammoniumphenylamino, 3-(2-sulfatoethylsulfonyl)phenylamino, 4-(2-sulfatoethylsulfonyl)phenylamino, 3-(vinylsulfonyl)phenylamino, 4-(vinylsulfonyl)-phenylamino, N-methyl-N-(2-(2-sulfatoethylsulfonyl)ethyl)amino, N-phenyl-N-(2-(2-sulfatoethylsulfonyl)ethyl)amino.

In the general formula (13) the radicals R²⁴ to R²⁶ are each preferably methyl or ethyl.

Anion B⁻ is preferably sulfate or chloride.

In the general formula (13), the quaternary ammonium group is preferably meta or para to the free bond on the benzene nucleus.

Examples of the group Z²¹ are 2,4-difluoropyrimidin-6-yl, 4,6-difluoropyrimidin-2-yl, 5-chloro-2,4-difluoropyrimidin-6-yl, 5-chloro-4,6-difluoropyrimidin-2-yl, 4,5-difluoro-pyrimidin-6-yl, 5-chloro-4-fluoropyrimidin-6-yl, 2,4,5-trichloropyrimidin-6-yl, 4,5-dichloropyrimidin-6-yl, 2,4-dichloropyrimidin-6-yl, 4-fluoropyrimidin-6-yl, 4-chloro-pyrimidin-6-yl, or a group of the general formula (9) with the above-indicated examples for Q¹ and Q² or 2,3-dichloroquinoxaline-6-carbonyl.

Z²¹ is preferably 2,4-difluoropyrimidin-6-yl, 4,6-difluoropyrimidin-2-yl, 5-chloro-2,4-difluoropyrimidin-6-yl, 5-chloro-4,6-difluoropyrimidin-2-yl or a group of the general formula (9) with the above-indicated preferred groups for Q¹ and Q².

With particular preference Z²¹ is 2,4-difluoropyrimidin-6-yl, 5-chloro-2,4-difluoropyrimidin-6-yl or a group of the general formula (9) with the above-indicated particularly preferred groups Q¹ and Q².

Preferred mixtures contain one or more dyes of the general formula (Ia)

and one or more dyes of the general formula (IIa)

plus if desired one or more dyes of the general formulae (IIIa) to (IIIf).

In the general formulae (Ia) and (IIa), M, A, R¹, Z, D³ and R are each as defined above.

In the general formula (Ia), it is particularly preferable for A to be phenylene and Z to be vinyl or β-sulfatoethyl.

In the general formula (Ia), it is most preferable for A to be phenylene, R¹ to be hydrogen and Z to be vinyl or β-sulfatoethyl.

The dye mixtures according to the invention contain bisazo dyes of the general formula (I) in an amount of 30 to 95% by weight and preferably 50 to 90% by weight and monoazo dyes of the general formula (II) in an amount of 5 to 70% by weight and preferably 10 to 50% by weight, and dyes of the general formulae (IIIa) to (IIIf) in an amount of 0 to 40% by weight, preferably 5 to 25% by weight.

Optionally, the dye mixtures according to the invention may also contain one or more monoazo dyes of the general formulae (15) or (16) in an amount of up to 10% by weight, preferably up to 5% by weight,

where M and D² are each as defined above. It is particularly preferable for D² to be 4-(2-sulfatoethylsulfonyl)phenyl or 4-vinylsulfonylphenyl.

Dyes of the general formula (I) are known from Eβ-A1046677, the dyes of the general formula (II) are known in part from WO 9610610, WO 9725377, WO 9947608 and EP-A 922735.

Dyes of the general formulae (15) and (16) are obtainable via standard synthetic methods or are in some instances formed during the synthesis of dyes of the general formula (I). They are customarily used as shading components.

The dye mixtures according to the invention can be present as a preparation in solid or liquid (dissolved) form. In solid form, they contain, to the extent necessary, the electrolyte salts customary in the case of water-soluble and especially fiber-reactive dyes, such as sodium chloride, potassium chloride and sodium sulfate, and may further contain the auxiliaries customary in commercial dyes, such as buffer substances capable of setting a pH in aqueous solution between 3 and 7, such as sodium acetate, sodium citrate, sodium borate, sodium bicarbonate, sodium dihydrogenphosphate and disodium hydrogenphosphate, dyeing auxiliaries, dustproofing agents and small amounts of siccatives; when they are present in a liquid, aqueous solution (including a content of thickeners of the type customary in print pastes), they may also contain substances which ensure a long life for these preparations, for example mold preventatives.

In solid form, the dye mixtures according to the invention are generally present as powders or granules which contain electrolyte salt and which will hereinbelow generally be referred to as a preparation with or without one or more of the abovementioned auxiliaries. In the preparations, the dye mixture is present at 10 to 90% by weight, based on the preparation containing it. The buffer substances are generally present in a total amount of up to 5% by weight, based on the preparation.

When the dye mixtures according to the invention are present in an aqueous solution, the total dye content of these aqueous solutions is up to about 50% by weight, for example between 5 and 50% by weight, the electrolyte salt content of these aqueous solutions preferably being below 10% by weight, based on the aqueous solution; the aqueous solutions (liquid preparations) can contain the aforementioned buffer substances in an amount which is generally up to 5% by weight and preferably up to 2% by weight.

The dye mixtures according to the invention are preparable in a conventional manner, as by mechanically mixing the individual dyes, whether in the form of their dye powders or granules or their as-synthesized solutions or in the form of aqueous solutions of the individual dyes generally, which may additionally contain customary auxiliaries, or by conventional diazotization and coupling of suitable mixtures of diazo and coupling components in the desired amount ratios.

For example, when the diazo components with the groups D² and D³ in the general formulae (I) and (II) possess the same meaning (D²=D³), an amine of the general formula (17) D²-NH₂   (17), where D² is as defined above can be diazotized in a conventional manner and the resulting diazonium compound then reacted in aqueous medium at a pH below 3 with a mixture of 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid or 4-amino-5-hydroxynaphthalene-1,7-disulfonic acid and an optionally N-substituted 6-amino-4-hydroxynaphthalene-2-sulfonic acid or 3-amino-5-hydroxynaphthalene-2,7-disulfonic acid to give a mixture of two red monoazo dyes of the formulae (15) and (II). Subsequently an amine of the general formula (18) D¹-NH₂   (18), where D² is as defined above is diazotized in a conventional manner and the resulting diazonium compound is then coupled in a second stage with the mixture of the monoazo dyes of the general formulae (15) and (II) obtained in the first stage, coupling taking place at a pH of between 3 and 7.5, to give a mixture of the dyes of the general formulae (I) and (II).

Alternatively, where the diazo components with the groups D¹ and D³ in the general formulae (I) and (II) possess the same meaning (D¹=D³), the dye mixture of the invention can be prepared by conventionally diazotizing an amine of the general formula (18), where D¹ is as defined in claim 1, and then reacting the resulting diazonium compound of an aqueous solution or suspension of a mixture of defined proportion of a red monoazo dye of the general formula (15) and an optionally substituted 6-amino-4-hydroxynaphthalene-2-sulfonic acid, first with a pH below 3 to give a mixture of two red monoazo dyes of the general formulae (15) and (II), and, when acidic coupling is at an end, by raising the pH to 4-7.5, carrying out the second coupling of the monoazo dye of the general formula (15), giving a mixture of the two dyes of the general formulae (I) and (II).

The red monoazo dyes of the general formula (15) can be prepared by conventionally diazotizing an amine of the general formula (17), where D² is as defined in claim 1, and then coupling the resulting diazonium compound in an aqueous medium at a pH below 2 with 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid and/or 4-amino-5-hydroxynaphthalene-1,7-disulfonic acid in a first stage.

The dye mixture of the invention is isolated in a conventional manner, where appropriate following the addition of one or more, such as two or three, yellow components of the general formulae (IIIa) to (IIIf), in solid form or as an aqueous solution, by salting out for example with sodium chloride or potassium chloride or by spray drying.

Additionally, the as-synthesized solutions of the dye mixtures of the general formula (I) and (II) can be used directly as a liquid preparation for dyeing, where appropriate following addition of one or more, such as two or three, yellow components of the general formulae (IIIa) to (IIIf) in solid form or as aqueous solutions and also, where appropriate, addition of a buffer substance and, where appropriate, after concentration or dilution.

Dye mixtures which as well as β-chloroethylsulfonyl or β-thiosulfatoethylsulfonyl or β-sulfatoethylsulfonyl groups also contain vinylsulfonyl groups as reactive radicals can be synthesized not only starting from appropriately substituted vinylsulfonylanilines or naphthylamines but also by reaction of a dye mixture where Z is β-chloroethyl, β-thiosulfatoethyl or β-sulfatoethyl with Man amount of alkali required for the desired fraction and converting the β-substituted ethylsulfonyl groups mentioned into vinylsulfonyl groups. This conversion is effected in a manner familiar to one skilled in the art.

The dye mixtures according to the invention have useful application properties. They are used for dyeing or printing hydroxyl- and/or carboxamido-containing materials, for example in the form of sheetlike structures, such as paper and leather or of films, for example composed of polyamide, or in bulk, as for example polyamide and polyurethane, but especially for dyeing and printing these materials in fiber form.

The present invention thus also provides for the use of the dye mixtures according to the invention for dyeing or printing these materials, or rather processes for dyeing or printing these materials in a conventional manner, by using a dye mixture according to the invention or its individual components (dyes) individually together as a colorant. The materials are preferably employed in the form of fiber materials, especially in the form of textile fibers, such as woven fabrics or yarns, as in the form of hanks or wound packages.

Hydroxyl-containing materials are those of natural or synthetic origin, for example cellulose fiber materials or their regenerated products and polyvinyl alcohols. Cellulose fiber materials are preferably cotton, but also other vegetable fibers, such as linen, hemp, jute and ramie fibers; regenerated cellulose fibers are for example staple viscose and filament viscose and also chemically modified cellulose fibers, such as aminated cellulose fibers or fibers as described for example in WO 96/37641 and WO 96/37642 and also in EP 0 538 785 and EP 0 692 559.

Carboxamido-containing materials are for example synthetic and natural polyamides and polyurethanes, especially in the form of fibers, for example wool and other animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-11 and nylon-4.

The dye mixtures according to the invention can be applied to and fixed on the substrates mentioned, especially the fiber materials mentioned, by the application techniques known for water-soluble dyes and especially for fiber-reactive dyes. For instance, on cellulose fibers they produce by the exhaust method from a long liquor and also from a short liquor, for example in a liquor to goods ratio of 5:1 to 100:1, preferably 6:1 to 30:1, using various acid-binding agents and optionally neutral salts as far as necessary, such as sodium chloride or sodium sulfate, dyeings having very good color yields. Application is preferably from an aqueous bath at temperatures between 40 and 105° C., optionally at a temperature of up to 130° C. under superatmospheric pressure, but preferably at 30 to 95° C., especially 45 to 65° C., in the presence or absence of customary dyeing auxiliaries. One possible procedure here is to introduce the material into the warm bath and to gradually heat the bath to the desired dyeing temperature and complete the dyeing process at that temperature. The neutral salts which accelerate the exhaustion of the dyes may also if desired only be added to the bath after the actual dyeing temperature has been reached.

Padding processes likewise provide excellent color yields and a very good color build-up on cellulose fibers, the dyes being fixable in a conventional manner by batching at room temperature or elevated temperature, for example at up to about 60° C., or in a continuous manner, for example by means of a pad-dry-pad steam process, by steaming or using dry heat.

Similarly, the customary printing processes for cellulose fibers, which can be carried out in one step, for example by printing with a print paste containing sodium bicarbonate or some other acid-binding agent and by subsequent steaming at 100 to 103° C., or in two steps, for example by printing with a neutral to weak acidic print color and then fixing either by passing the printed material through hot electrolyte-containing alkaline bath or by overpadding with an alkaline electrolyte-containing padding liquor and subsequent batching of the alkali-overpadded material or subsequent steaming or subsequent dry heat treatment of the alkali-overpadded material, produce strong prints with well-defined contours and a clear white ground. The outcome of the prints is little affected, if at all, by variations in the fixing conditions.

When fixing by means of dry heat in accordance with the customary thermofix processes, hot air at 120 to 200° C. is used. In addition to the customary steam at 101 to 103° C., it is also possible to use superheated steam and high-pressure steam at temperatures of up to 160° C.

The acid-binding agents which effect the fixation of the dyes of the dye mixtures according to the invention on the cellulose fibers are for example water-soluble basic salts of alkali metals and likewise alkaline earth metals of inorganic or organic acids or compounds which liberate alkali in the heat, and also alkali metal silicates. Especially suitable are the alkali metal hydroxides and alkali metal salts of weak to medium inorganic or organic acids, the preferred alkali metal compounds being the sodium and potassium compounds. Such acid-binding agents are for example sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogenphosphate, disodium hydrogenphosphate, sodium trichloroacetate, trisodium phosphate or waterglass or mixtures thereof, for example mixtures of aqueous sodium hydroxide solution and waterglass.

The dye mixtures according to the invention are notable for outstanding color strength when applied to the cellulose fiber materials by dyeing or printing in the presence of no or very small amounts of alkali or alkaline earth metal compounds. For instance, no electrolyte salt is required for a shallow depth of shade, not more than 5 g/l of electrolyte salt is required for a medium depth of shade and not more than 10 g/l of electrolyte salt is required for deep shades.

According to the invention, a shallow depth of shade refers to the use of 2% by weight of dye based on the substrate to be dyed, a medium depth of shade refers to the use of 2 to 4% by weight based on the substrate to be dyed and a deep shade refers to the use of 4 to 10% by weight of dye based on the substrate to be dyed.

The dyeings and prints obtainable with the dye mixtures according to the invention possess bright shades; more particularly, the dyeings and prints on cellulose fiber materials possess good lightfastness and especially good wetfastnesses, such as fastness to washing, milling, water, seawater, crossdyeing and acidic and alkaline perspiration, also good fastness to pleating, hotpressing and rubbing. Furthermore, the cellulose dyeings obtained following the customary aftertreatment of rinsing to remove unfixed dye portions exhibit excellent wetfastnesses, in particular since unfixed dye portions are easily washed off because of their good solubility in cold water.

Furthermore, the dye mixtures according to the invention can also be used for the fiber-reactive dyeing of wool. Moreover, wool which has been given a nonfelting or low-felting finish (cf. for example H. Rath, Lehrbuch der Textilchemie, Springer-Verlag, 3rd edition (1972), pages 295-299, especially finished by the Hercosett process (page 298); J. Soc. Dyers and Colourists 1972, 93-99, and 1975, 33-44), can be dyed to very good fastness properties. The process of dyeing on wool is here carried out in a conventional manner from an acidic medium. For instance, acetic acid and/or ammonium sulfate or acetic acid and ammonium acetate or sodium acetate can be added to the dyebath to obtain the desired pH. To obtain a dyeing of acceptable levelness, it is advisable to add a customary leveling agent, for example a leveling agent based on a reaction product of cyanuric chloride with three times the molar amount of an aminobenzenesulfonic acid and/or of an aminonaphthalenesulfonic acid or on the basis of a reaction product of for example stearylamine with ethylene oxide. For instance, the dye mixture according to the invention is preferably subjected to the exhaust process initially from an acidic dyebath having a pH of about 3.5 to 5.5 under pH control and the pH is then, toward the end of the dyeing time, shifted into the neutral and optionally weakly alkaline range up to a pH of 8.5 to bring about, especially for very deep dyeings, the full reactive bond between the dyes of the dye mixtures according to the invention and the fiber. At the same time, the dye portion not reactively bound is removed.

The procedure described herein also applies to the production of dyeings on fiber materials composed of other natural polyamides or of synthetic polyamides and polyurethanes. In general, the material to be dyed is introduced into the bath at a temperature of about 40° C., agitated therein for some time, the dyebath is then adjusted to the desired weakly acidic, preferably weakly acetic acid, pH and the actual dyeing is carried out at a temperature between 60 and 98° C. However, the dyeings can also be carried out at the boil or in sealed dyeing apparatus at temperatures of up to 106° C. Since the water solubility of the dye mixtures according to the invention is very good, they can also be used with advantage in customary continuous dyeing processes. The color strength of the dye mixtures according to the invention is very high.

The dye mixtures according to the invention dye the materials mentioned, preferably fiber materials, in navy to jet black shades having good fastness properties.

The examples hereinbelow serve to illustrate the invention. Parts and percentages are by weight, unless otherwise stated. Parts by weight relate to parts by volume as the kilogram relative to the liter. The compounds described in the examples in terms of a formula are indicated in the form of the sodium salts, since they are generally prepared and isolated in the form of their salts, preferably sodium or potassium salts, and used for dyeing in the form of their salts. The starting compounds described in the examples hereinbelow can be used in the synthesis in the form of the free acid or likewise in the form of their salts, preferably alkali metal salts, such as sodium or potassium salts.

EXAMPLE 1

70 parts of an electrolyte-containing dye powder containing the navy disazo dye of the formula (IA)

in a 70% fraction, 20 parts of an electrolyte-containing dye powder containing the orange-red monoazo dye of the formula (IIA)

in a 75% fraction and 10 parts of an electrolyte-containing dye powder containing the yellow disazo dye of the formula (IIIf-1)

in a 70% fraction are mechanically mixed with each other.

The resulting dye mixture according to the invention provides jet black dyeings and prints, on cotton for example, under the dyeing conditions customary for reactive dyes.

EXAMPLE 2

70 parts of an electrolyte-containing dye powder containing the navy disazo dye of the formula (IA) in a 70% fraction, 20 parts of an electrolyte-containing dye powder containing the red monoazo dye of the formula (IIB)

in an 80% fraction and 10 parts of an electrolyte-containing dye powder containing the yellow disazo dye of the formula (IIIc-1)

in a 70% fraction are dissolved in 500 parts of water and the resulting dye solution is adjusted to pH 5.5-6.5. Evaporation or spray drying of this dye solution provides a dye mixture which provides jet black dyeings and prints on cotton under the dyeing conditions customary for reactive dyes.

EXAMPLE 3

a) 281 parts of 4-(β-sulfatoethylsulfonyl)aniline are suspended in 650 parts of ice-water and 180 parts of 30% hydrochloric acid and diazotized by dropwise addition of 173 parts of 40% sodium nitrite solution. 223 parts of 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid and 72 parts of 6-amino-4-hydroxynaphthalene-2-sulfonic acid are added and coupled in a first step at pH 1-1.8 at below 20° C. to form a mixture of two red monoazo dyes conforming to the formulae (15-1) and (IIC). The stated pH range is set and maintained during the coupling reaction by addition of a total of about 1 50 parts of sodium bicarbonate.

b) In a second, separate reaction vessel, 280 parts of 4-amino-N-(3-((β-sulfatoethyl)-sulfonyl)phenyl)benzamide are suspended in 1 600 parts of ice-water, adjusted to pH 6.5-7 with about 35 parts of sodium carbonate and admixed with 122 parts of 40% sodium nitrite solution. This suspension is added dropwise to a mixture of 450 parts of ice, 350 parts of ice-water and 255 parts of concentrated hydrochloric acid. After subsequent stirring at 5-10° C. for 2 hours, the excess nitrite is reduced with amidosulfonic acid and the resulting diazo suspension is pumped into the mixture of red monoazo dyes of a). Subsequently, at below 25° C., the reaction mixture is adjusted to a pH of 5-6 with sodium carbonate and, after the end of the coupling reaction, 1 10 parts of the yellow monoazo dye of the formula (IIIa-1) are added in the form of an aqueous solution to this reaction mixture, and the resulting 73:16:10 mixture of the dyes (IB), (IIC) and (IIIa-1) is isolated by spray drying.

Alternatively, the dye solution obtained can also be buffered at pH 5.5-6 by addition of a phosphate buffer and be adjusted by further dilution or concentration to provide a liquid brand of defined strength.

The resulting dye mixture according to the invention dyes cotton in black shades.

EXAMPLE 4

a) 178 parts of 4-(β-sulfatoethylsulfonyl)aniline are suspended in 420 parts of ice-water and 115 parts of 30% hydrochloric acid and diazotized by dropwise addition of 110 parts of 40% sodium nitrite solution. 201 parts of 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid are added and coupled in a first step at pH 1 to 1.3 at below 20° C. to form a red monoazo dye of formula (15-1). The stated pH range is set and maintained during the coupling reaction by addition of a total of about 90 parts of sodium bicarbonate.

b) In a second, separate reaction vessel, 353 parts of 4-amino-N-(3-((β-sulfatoethyl)-sulfonyl)phenyl)benzamide are suspended in 1950 parts of ice-water, adjusted to pH 6.5-7 with about 65 parts of sodium carbonate and admixed with 1 54 parts of 40% sodium nitrite solution. This suspension is added dropwise to a mixture of 550 parts of ice, 450 parts of ice-water and 320 parts of concentrated hydrochloric acid. After subsequent stirring at 5-10° C. for 2 hours, the excess nitrite is reduced with amidosulfonic acid and the resulting diazo suspension is pumped into the solution of the red monoazo dye of a). This reaction mixture is then admixed with 80 parts of 3-amino-5-hydroxynapthalene. 2,7-disulfonic acid.

Subsequently, at below 25° C., the pH is first adjusted to 1.5-2.5 using sodium bicarbonate and maintained, with acidic coupling to 3-amino-5-hydroxynapthalene-2,7-disulfonic acid producing a red monoazo dye of the formula (IID). After the end of acidic coupling a pH of 5-6 is established by adding sodium carbonate and the reaction mixtured obtained after the end of the second coupling reaction of the monoazo dye of the formula (15-1) is admixed with 100 parts of the yellow disazo dye of the formula (IIIe-1).

The resulting 70:20:10 mixture of the dyes (IB), (IID) and (IIIe-1) is isolated by spray drying.

The resulting dye mixture according to the invention dyes cotton in black shades.

EXAMPLE 5

406 parts of 4-amino-N-(3-((β-sulfatoethyl)sulfonyl)phenyl)benzamide are suspended in 2250 parts of ice-water, the suspension is adjusted to a pH of 6.5-7 with about 75 parts of sodium carbonate and 177 parts of 40% sodium nitrite solution are added. This suspension is added dropwise to a mixture of 630 parts of ice, 520 parts of ice-water and 370 parts of concentrated hydrochloric acid. After subsequent stirring at 5-10° C. for 2 hours, the excess nitrite is reduced with amidosulfonic acid and the resulting diazo suspension is pumped into an aqueous solution of 426 parts of the red monoazo dye of the formula (15-1), prepared as described in example 4a). This reaction mixture is then admixed with 80 parts of 3-amino-5-hydroxynaphthalene-2,7-disulfonic acid and 38 parts of 5-hydroxy-1-(4-sulfophenyl)-1H-pyrazole-3-carboxylic acid. Subsequently, at below 25° C., the pH is first adjusted to 1.5-2.5 with sodium bicarbonate and maintained, with acidic coupling producing a red monoazo dye of the formula (IID). After the end of acidic coupling sodium carbonate is added to set a pH of 5-6 and the 70:20:10 mixture of the dyes (IB), (IID) and (IIIc-1) formed after the end of the second coupling reaction is isolated by spray drying.

The resulting dye mixture according to the invention dyes cotton in black shades.

EXAMPLE 6

350 parts of 4-amino-N-(4-((β-sulfatoethyl)sulfonyl)phenyl)benzamide are suspended in 2000 parts of ice-water, the pH of the suspension is adjusted to 6.5-7 using about 44 parts of sodium carbonate, and 152 parts of 40% sodium nitrite solution are added. This suspension is added dropwise to a mixture of 560 parts of ice, 440 parts of ice-water and 320 parts of concentrated hydrochloric acid. After subsequent stirring at 5-10° C. for 2 hours, the excess nitrite is reduced with amidosulfonic acid and the resulting diazo suspension is pumped into an aqueous mixture of 474 parts of the red monoazo dye (15-1) and 173 parts of the red monoazo dye of the formula (IIC), prepared in analogy to example 3a). This reaction mixture is admixed with 44 parts of 4-(5-hydroxy-3-methylpyrazol-1-yl)benzenesulfonic acid and subsequently adjusted to a pH of 5-6 at below 25° C. With sodium carbonate. After the end of the coupling reaction the resultant 73:16:11 mixture of the three dyes (IA), (IIC) and (IIIc-2) is isolated by spray drying.

Alternatively, the dye solution obtained can also be buffered at pH 5.5-6 by addition of a phosphate buffer and adjuted by further dilution or further concentration to provide a liquid brand of defined strength.

The resulting dye mixture according to the invention dyes cotton in black shades.

EXAMPLE 7

a) 281 parts of 4-(β-sulfatoethylsulfonyl)aniline are suspended in 650 parts of ice-water and 180 parts of 30% hydrochloric acid and diazotized by dropwise addition of 173 parts of 40% sodium nitrite solution. 174 parts of 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 87 parts of 6-amino-4-hydroxynaphthalene-2-sulfonic acid and 17 parts of 2,4-diaminobenzenesulfonic acid are added and coupled in a first step at pH 1-1.8 at below 20° C. to form a mixture of three monoazo dyes conforming to the formulae (15-1), (IIC) and (IIIa-1). The stated pH range is set and maintained during the coupling reaction by addition of solid sodium bicarbonate.

b) In a second, separate reaction vessel, 255 parts of 4-amino-N-(3-((β-sulfatoethyl)-sulfonyl)phenyl)benzamide are suspended in 1500 parts of ice-water, adjusted to pH 6.5-7 with about 32 parts of sodium carbonate and admixed with 111 parts of 40% sodium nitrite solution. This suspension is added dropwise to a mixture of 410 parts of ice, 320 parts of ice-water and 235 parts of concentrated hydrochloric acid. After subsequent stirring at 5-10° C. for 2 hours, the excess nitrite is reduced with amidosulfonic acid and the resulting diazo suspension is pumped into the mixture of the three monoazo dyes of a). Subsequently, at below 25° C., the pH is adjusted to 5-6 using sodium carbonate and the 67:23:10 mixture of the dyes (IB), (IIC) and (IIIb-1) obtained after the end of the second coupling reaction is isolated by spray drying.

The resulting dye mixture according to the invention dyes cotton in black shades.

EXAMPLES 8 TO 159

The table examples hereinbelow describe further inventive mixtures of the dyes of the general formulae (I) to (III), each recited in the form of the sodium salts. The mixing ratios are indicated in percent by weight. The dye mixtures provide black dyeings, on cotton for example, by the dyeing methods customary for reactive dyes. Example Dye of gen. formula (I) Dye of gen. formula (II)  8 (IA)

 9 (IA)

10 (IA)

11 (IA)

12 (IA)

13 (IA)

14 (IA)

15 (IA)

16 (IA)

17 (IA)

18 (IA)

19 (IA)

20 (IA)

21 (IA)

22 (IA)

23 (IA)

24 (IA)

25 (IA)

26 (IA)

27 (IA)

28 (IA)

29 (IA)

30 (IA)

31 (IA)

Ratio Example Dye of gen. formula (III) (I):(II):(III)  8

67:20:13  9

70:20:10 10

72:18:10 11

67:18:15 12

66:20:14 13

70:20:10 14

75:15:10 15

70:18:12 16

65:20:15 17

66:20:14 18

68:20:12 19 (IIIf-1) 70:20:10 20 (IIIf-2) 75:15:10 21

65:20:15 22 (IIIf-2) 68:22:10 23 (IIIf-1) 70:20:10 24 (IIIc-1) 72:18:10 25 (IIIb-3) 75:15:10 26

70:20:10 27

77:13:10 28 (IIIe-1) 73:17:10 29 (IIIa-1) 68:22:10 30 (IIIb-2) 70:20:10 31 (IIIb-3) 72:20:8 

EXAMPLES 32-57

Repetition of Examples 1, 2 and 8-31 using dye (IB) instead of dye (IA).

EXAMPLES 58-83

Repetition of Examples 1, 2 and 8-31 using dye (IC) instead of dye (IA):

EXAMPLES 84-109

Repetition of Examples 1, 2 and 8-31 using dye (ID) instead of dye (IA):

EXAMPLES 110-135

Dye mixtures according to Example 3 Dye of gen. Dye of gen. Dye of gen. Example formula (I) formula (II) formula (III) Ratio (I):(II):(III) 136 (IA) (IIC) (IIIf-1) 75:15:10 137 (IB) (IIG) (IIIc-1) 68:22:10 138 (IC) (IIC) (IIIb-2) 72:18:10 139 (IC) (IIG) (IIIe-1) 70:20:10 140 (ID) (IIC) (IIIa-1) 73:16:11 141 (ID) (IIG) (IIIf-1) 74:16:10 142 (IE) (IIC) (IIIb-3) 75:15:10 143 (IE) (IIG) (IIIf-2) 73:17:10

Dye mixtures according to Example 4 Dye of gen. Ratio Example Dye of gen. formula (I) Dye of gen. formula (II) formula (III) (I):(II):(III) 144 (IA)

(IIIb-3) 72:18:10 145 (IB)

(IIIc-1) 72:16:12 146 (IC)

(IIIa-1) 70:20:10 147 (ID)

(IIIf-1) 73:17:10 148

(IIC) (IIIf-1) 72:18:10 149 (IF) (IIG) (IIIe-1) 70:20:10 150

(IIC) (IIIb-2) 71:18:11 151 (IG) (IIG) (IIIc-1) 75:15:10 152

(IIC) (IIIb-3) 73:17:10 153 (IH) (IIG) (IIIf-3) 70:18:12 154

(IIC) (IIIa-2) 76:14:10 155 (IJ) (IIG) (IIIf-4) 70:17:13

Dye mixtures according to Example 7 Dye of gen. Dye of gen. Example formula (I) formula (II) Dye of gen. formula (III) Ratio (I):(II):(III) 156 (IB) (IIG) (IIIb-1) 73:17:10 157 (IF) (IIAG)

75:15:10 158 (IG) (IID)

72:18:10 159 (IG) (IIAH) (IIIb-5) 70:20:10

USE EXAMPLE 1

2 parts of a dye obtained according to example 1-7 are dissolved in 999 parts of water and 5 parts of sodium carbonate, 0,7 part of sodium hydroxide (in the form of a 32.5% aqueous solution) and optionally 1 part of a wetting agent are added. This dyebath is entered with 100 g of a cotton fabric. The temperature of the dyebath is first maintained at 25° C. for 10 minutes, then raised over 30 minutes to the final temperature (40-60° C.) and maintained at that level for a further 60-90 minutes. Thereafter, the dyed material is rinsed initially with tap water for 2 minutes and then with ion-free water for 5 minutes. The dyed material is neutralized at 40° C. in 1000 parts of an aqueous solution containing 1 part of 50% acetic acid for 10 minutes. It is subsequently rinsed with ion-free water at 70° C. and thereafter soaped off at the boil with a detergent for 15 minutes, rinsed once more and dried. This gives a strong navy to gray dyeing having very good fastness properties.

USE EXAMPLE 2

4 parts of a dye obtained according to example 1-7 and 5 parts of sodium chloride are dissolved in 999 parts of water, 5 parts of sodium carbonate, 0.7 part of sodium hydroxide (in the form of a 32.5% aqueous solution) and optionally 1 part of a wetting agent are added. This dyebath is entered with 100 g of a cotton fabric. The rest of the processing is as indicated in use example 1. This gives a strong navy to black dyeing having very good fastness properties.

USE EXAMPLE 3

8 parts of a dye obtained according to example 1-7 and 10 parts of sodium chloride are dissolved in 997 parts of water, 5 parts of sodium carbonate, 1.3 parts of sodium hydroxide (in the form of a 32.5% aqueous solution) and optionally 1 part of a wetting agent are added. This dyebath is entered with 100 g of a cotton fabric. The rest of the processing is as indicated in use example 1. This gives a jet black dyeing having very good fastness properties. 

1. A reactive dye mixture comprising one or more dyes of the hereinbelow indicated and defined general formula (I),

one or more dyes of the hereinbelow indicated and defined general formula (II)

and, optionally, as further components for blending or shading, one or more dyes having, for example, the hereinbelow indicated and defined general formulae (IIIa)-(IIIf)

where: D¹ and D² are each a group of the general formula (1)

where R¹ is hydrogen, (C₁-C₄)-alkyl, aryl or a substituted aryl radical; R² and R³ are independently hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; and A is a phenylene group of the general formula (2)

where R⁴ and R⁵ are independently hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; or a naphthylene group of the general formula (3)

where R⁶ and R⁷ are independently hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; or a polymethylene group of the general formula (4) —(CR⁸R⁹)_(k)—  (4) where k is an integer greater than 1 and R⁸ and R⁹ are independently hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, hydroxyl, cyano, amido, halogen or aryl; and X¹ is hydrogen or a group of the formula —SO₂-Z; or are each a phenyl group of the general formula (5)

where ¹⁰ and R¹¹ are independently hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; and X² has one of the meanings of X¹; or are each a naphthyl group of the general formula (6)

where R¹² and R¹³ are independently hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; and X³ has one of the meanings of X¹; Z is —CH═CH₂, —CH₂CH₂Z¹ or hydroxyl, where Z¹ is hydroxyl or an alkali-eliminable group; and M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal; D³ has one of the meanings of D¹ or D² or is a group of the general formula (7)

where R²¹ and R²² independently have one of the meanings of R² and R³; R²³ is hydrogen, (C₁-C₄)-alkyl, unsubstituted or (C₁-C₄)-alkyl-, (C₁-C₄)-alkoxy-, sulfo-, halogen- or carboxyl-substituted phenyl; and Z²¹ is a fiber-reactive heterocyclic group; R is hydrogen, (C₁-C₄)-alkyl or phenyl which is unsubstituted or substituted by (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, sulfo, halogen, carboxyl, acetamido or ureido; or is a group of the formula (14) CH₂—SO₃M   (14), where M is as defined above; and n is 1 or 2, D⁴, D⁵, D⁶, D⁷ and D⁸ have one of the meanings of D¹, D² or D³, and, if R³¹ is not a group of the general formula (8) or (9), D⁴, and also D⁵ or D⁶ and D⁸, contain at least one fiber-reactive group of the formula —SO₂Z or Z²¹; R³¹ is hydrogen, acetyl, carbamoyl, sulfomethyl or a group of the general formula (8) or (9), R³² is hydrogen or sulfomethyl, R³³ is methyl, carboxyl or carboxyalkyl, with C₁-C₄-alkyl, R³⁴ is hydrogen or methyl, R³⁵ is hydrogen, cyano, carbamoyl, carboxyl or sulfomethyl, R³⁶ is methyl, ethyl or B3-sulfoethyl, R³⁷ is methyl, carboxyl or carboxyalkyl, with C₁-C₄-alkyl, R³⁸ is acetamido, ureido or methyl, R³⁹ is hydrogen, methyl or methoxy, m is 0 or 1, p is 1, 2 or 3, and Z³ has one of the meanings of Z²¹, where in the general formula (I) at least one of D¹ and D² is a group of the general formula (1); and when A is a group of the general formula (4), R¹ is aryl or substituted aryl; and the reactive dye of the general formula (I) contains at least one —SO₂-Z group.
 2. The dye mixture as claimed in claim 1, wherein the heterocyclic reactive group Z²¹ is a fiber-reactive group of the general formula (8) or (9) or (10)

where V is fluorine or chlorine; U¹, U² are independently fluorine, chlorine or hydrogen; and Q¹ , Q² are independently chlorine, fluorine, cyanamido, hydroxyl, (C₁-C₆)-alkoxy, phenoxy, sulfophenoxy, mercapto, (C₁-C₆)-alkylmercapto, pyridino, carboxypyridino, carbamoylpyridino or a group of the general formula (11) or (12)

where R^(2′) is hydrogen or (C₁-C₆)-alkyl, sulfo-(C₁-C₆)-alkyl, or phenyl which is unsubstituted or substituted by (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, sulfo, halogen, carboxyl, acetamido or ureido; R^(3′) and R^(4′) independently have one of the meanings of R^(2′), or combine to form a cyclic ring system of the formula —(CH₂)_(j)—, where j is 4 or 5, or alternatively —(CH₂)₂-E-(CH₂)₂—, where E is oxygen, sulfur, sulfo, —NR⁵—, where R^(5′) is equal to (C₁-C₆)-alkyl, or they are a group of the general formula (13)

where R²⁴, R²⁵ and R²⁶ are each (C₁-C₄)-alkyl or (C₁-C₄)-hydroxyalkyl; and B⁻ is the equivalent of an anion, such as hydrogensulfate, sulfate, fluoride, chloride, bromide, dihydrogenphosphate, hydrogenphosphate, phosphate, hydroxide or acetate; W is phenylene which is unsubstituted or substituted by 1 or 2 substituents, such as (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, carboxyl, sulfo, chlorine, bromine, or is (C₁-C₄)-alkylene-arylene or (C₂-C₆)-alkylene, which can be interrupted by oxygen, sulfur, sulfo, amino, carbonyl, carboxamido, or is phenylene-CONH-phenylene, which is unsubstituted or substituted by (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, hydroxyl, sulfo, carboxyl, amido, ureido or halogen, or is naphthylene, which is unsubstituted or substituted by one or two sulfo groups; and Z is as in claim
 1. 3. The reactive dye mixture as claimed in claim 1, wherein the substituents R¹ to R⁵, R⁸ to R¹¹ and R²³ are each hydrogen, R⁶, R⁷, R¹², R¹³, R²¹ and R²² are each hydrogen or sulfo and R²⁴, R²⁵ and R²⁶ are each methyl.
 4. The reactive dye mixture as claimed in claim 1, wherein Z is vinyl, β-chloroethyl or β-sulfatoethyl.
 5. The reactive dye mixture as claimed in claim 1, wherein the groups Q¹ and Q² in the general formula (9) independently of one another are fluorine, chlorine, cyanamido, morpholino, 2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, 3-trimethylammoniumphenylamino, 4-trimethylammoniumphenylamino, 3-(2-sulfatoethylsulfonyl)phenylamino, 4-(2-sulfatoethylsulfonyl)phenylamino, 3-(vinylsulfonyl)phenylamino, 4-(vinylsulfonyl)phenylamino, N-methyl-N-(2-(2-sulfatoethylsulfonyl)ethyl)amino or N-phenyl-N-(2-(2-sulfatoethylsulfonyl)ethyl)amino.
 6. The reactive dye mixture as claimed in claim 1, comprising at least one dye of the general formula (Ia)

and at least one dye of the general formula (IIa)

where M, A, R¹, Z, D³ and R are each as defined in claim
 1. 7. The reactive dye mixture as claimed in claim 6, wherein, in formula (Ia), A is phenylene and Z is vinyl or β-sulfatoethyl and, in formula (IIa), R is hydrogen or sulfomethyl and D³ has one of the meanings of D¹ or D² or is a group of the general formula (7)

where R²¹ and R²² independently have one of the meanings of R² and R³: R²³ is hydrogen, (C₁-C₄)-alkyl, unsubstituted or (C₁-C₄)-alkyl-, (C₁-C₄)-alkoxy-, sulfo-, halogen- or carboxyl-substituted phenyl; and Z²¹ is a fiber-reactive heterocyclic group;
 8. The reactive dye mixture as claimed in claim 1, comprising a dye of the formula (I) in a fraction of 30 to 95% by weight and a dye of the formula (II) in a fraction of 5 to 70% by weight.
 9. The reactive dye mixture as claimed in claim 8, further comprising at least one dye of the formulae (IIIa) to (IIIf) in a fraction of 3 to 50% by weight.
 10. The reactive dye mixture as claimed in claim 1, comprising one or more monoazo dyes of the formula (15) and/or one or more monoazo dyes of the formula (16) each at 0.5 to 6% by weight

where D and M are each as defined in claim
 1. 11. The reactive dye mixture as claimed in claim 1, comprising more than one navy disazo dye of the general formula (I) in a fraction of up to 95% by weight.
 12. A process for producing dye mixtures as claimed in claim 1, which comprises mixing the individual dyes of the formulae (I) and (II) and, if used, (III) with each other either mechanically in solid form or in the form of the aqueous solutions.
 13. A process for producing dye mixtures as claimed in claim 1, where the diazo components with the groups D² and D³ in the general formulae (I) and (II) are the same, which comprises diazotizing an amine of the general formula (17) D²-NH²   (17), where D² is as defined in claim 1, and then reacting the resulting diazonium compound with a mixture of 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid or 4-amino-5-hydroxynaphthalene-1,7-disulfonic acid and an optionally N-substituted 6-amino-4-hydroxynaphthalene-2-sulfonic acid or 3-amino-5-hydroxynaphthalene-2,7-disulfonic acid to give the monoazo dyes of the formulae (15) and (II)

where D² and M are each as defined in claim 1, and then diazotizing an amine of the general formula (18) D¹-NH₂   (18), where D¹ is as defined in claim 1, and then coupling the resulting diazonium compound in a second stage with the mixture of the monoazo dyes of the general formulae (15) and (II) obtained in the first stage to give a mixture of the dyes of the general formulae (I) and (II).
 14. A process for producing dye mixtures as claimed in claim 1, where the diazo components with the groups D¹ and D³ in the general formulae (I) and (II) are the same, which comprises diazotizing an amine of the general formula (18), D¹-NH₂   (18), where D¹ is as defined in claim 1, and then reacting the resulting diazonium compound with a mixture of defined proportion of a red monoazo dye of the general formula (15)

where D² and M are each as defined in claim 1, and an optionally N-substituted 6-amino-4-hydroxynaphthalene-2-sulfonic acid or 3-amino-5-hydroxynaphthalene-2,7-disulfonic acid in a first stage to give a mixture of monoazo dyes of the general formulae (15) and (II) and then carrying out the second coupling of the monoazo dye of the general formula (15) to give a mixture of the two dyes of the general formulae (I) and (II).
 15. An aqueous liquid preparation comprising a dye mixture as claimed in claim 1 with a total dye content of 5-50% by weight.
 16. (canceled)
 17. The reactive dye mixture as claimed in claim 2, wherein the substituents R¹ to R⁵, R⁸ to R¹¹ and R²³ are each hydrogen, R⁶, R⁷, R¹², R¹³, R²¹ and R²² are each hydrogen or sulfo and R²⁴, R²⁵ and R²⁶ are each methyl and Z is vinyl, β-chloroethyl or β-sulfatoethyl.
 18. The reactive dye mixture as claimed in claim 17, wherein the groups Q¹ and Q² in the general formula (9) independently of one another are fluorine, chlorine, cyanamido, morpholino, 2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, 3-trimethylammoniumphenylamino, 4-trimethylammoniumphenylamino, 3-(2-sulfatoethylsulfonyl)phenylamino, 4-(2-sulfatoethylsulfonyl)phenylamino, 3-(vinylsulfonyl)phenylamino, 4-(vinylsulfonyl)phenylamino, N-methyl-N-(2-(2-sulfatoethylsulfonyl)ethyl)amino or N-phenyl-N-(2-(2-sulfatoethylsulfonyl)ethyl)amino.
 19. The reactive dye mixture as claimed in claim 18, comprising a dye of the formula (I) in a fraction of 30 to 95% by weight and a dye of the formula (II) in a fraction of 5 to 70% by weight.
 20. The reactive dye mixture as claimed in claim 19, further comprising at least one dye of the formulae (IIIa) to (IIIf) in a fraction of 3 to 50% by weight.
 21. A process of dyeing and printing hydroxyl- and/or carboxamido-containing fiber material which comprises contacting said material with the reactive dye mixture of claim
 1. 